Compositions containing synthetic resins



Patented Aug. 1o, 1931 FUNITED STATES PATENT err-Ice Qarleton Ellis, Montclalr,.N. 1., assignor to nuu- Foster Company, a corporation of New Jersey No Drawing. Application November 80, 1931,

- Serial No. 578,219

m Claims. (01. 260-4) Coal tar has long been recognized asthe source of many surprising and valuable chemical derivatives. Despite the variety of raw materials avail- 'able in petroleum its application or adaptation 5 to fields outside of its customary uses as a fuel,

lubricant or wax has made little progress.

It is an object of the present invention, which relates to synthetic resins and plastics from petroleum, to-extend the field of petroleum to boundl aries quite remote from those which confine its obvious uses.

The invention in one phase is concerned with the oxidation of petroleum hydrocarbons by air or an oxygen-containing gas to supply not only l special fuels having" desirable properties during combustion, but also certain products of oxidation which can be resinified to yield valuable plastics.

By petroleum hydrocarbons I include not only 2n the various earth oils, asphalts and the like, but

also shale, gilsonite and similar deposits and the various distillates or fractions obtained therefrom by heat or other means of separation; such fractions of course including hydrocarbon gases of 25 petroleum origin.

In my copending application Serial No. 743,453, Process of cracking and oxidizing oils, filed Oct. 13, 1924 now Patent 2,043,992, which applicationis derived from subject matter similar to that of Patent 1,517,968, patented December 2, 1924, ene titled Cracking and omdizing petroleum oil to make gasoline and useful products of oxidation, I have referred to the production of aldehydes by the oxidation of, petroleum and also to the deriva- 35 tion of resinous substances by the process described therein.

The present invention is a continuation in part of copendlng application Serial No. 5,634,

filed January 29, 1925, entitled Petroleum oxida- 49 tion products and their utilization, now Patent 1,697,266, and is in part concerned with the evaluation or utilization of petroleum aldehydes, as the aldehydic bodies obtained by the oxidation of petroleum hydrocarbons" may be termed; such cially available form with the least possible demand on raw materials from extraneous sources.

so In other words I am to utilize along with the aldehydes other bodies such as phenoloid compounds and the like appropriate for the purpose and to such an extent as they are thus obtainable, preferably only supplementing such supplies of essential raw material from petroleum by drawing on 5 outside sources to supply any deficiencies.

Substances which, under the desired temperature and pressure of operation, will exist in a liquid state or sufllciently fiuent to allow air or other oxidizing gas to bubble through are best 10 adapted to my process. Preferably there is maintained a deep layer or pool of the liquid or liquefied raw material into which air is injected near the bottom and rising through the liquid, preferably in small bubbles, supplies oxygen to the latter while effecting a desirable degree of agitation creating a circulation which brings all portions of the liquid into proximity of the air jets or currents. Agitation by special mechanical devices is not precluded but is not recommended for high pressure operations. The substances which I particularly propose to treat to obtain aldehydes and other products employed in accordance with my invention are in general hydrocarbon mixtures of low grade such as crude petroleum and its variousdistillates, natural gas, shale products and'the tars, pitches, sludges and residues of the petroleum industry; likewise oilsfrom the destructive distillation of coal, coal tar and residues, pitches, asphaltlc oils, malthas, asphalt, cracked oils and residues of cracking stills, wood tar oils and wood tars, peat distillates, lignite distillates, Montan and other waxes, especially in their 'cruder forms; also oils containing suspensions of solid substances such as powdered coal (colloidal fuel) peat. coke and other oxidizable or non-oxidizable finely-divided suspensions or emulsions. The treatment of pure or refined products such as anthracene or of substances already oxidized or normally containing 40 oxygen is not precluded. Thus I may treat lactic acid, glycerol, animal and vegetable oils and fats, stearine, stearine pitch or candle tar, stearic and oleic acids or other higher fatty acids by my process.

The-step of oxidation therefore is especiallyapplicable to the treatment of petroleum hydrocarbons in aliquld state, by bubbling the gaseous oxidizing agent therethrough under heat and pressure, permitting in a simple and efllcient 5 manner the establishment of the preferred oxidizingconditions wherein the substance to be oxi- 'dized is present in predominant proportions; thus reducing to a the occurrence of ordinary Y combustion and substantially eliminating the 55 hazard of explosive conditions which might prevail with oxygen present in much greater proportions. o

Moreover the oxidation step is applicable to petroleum hydrocarbons, including shale oil by drocarbons, natural gas, and the like, containing a considerable proportion of sulphur as the oxygen serves as a desulphurizing agent, forming sulphur dioxide and yielding distillates of relatively low. sulphur content. This tends to simplify refining operations involving" the removal of sulphur. The by-product sulphurdioxide may be recovered as liquid sulphur dioxide, as sul' phites or blsulphites or it may be converted into sulphuric acid and used in f refinery operations. The oxidation of sulphur -to sulphur dioxlde'is favorable from another standpoint, namely, that it furnishes heat which contributes to the maintenance of the temperature of the reaction chamber. Thus the phase of the oxidation process is advantageous not only from the desulphurizing standpoint but from that of securing heat by destroying a. baneful substance which should in any event be eliminated; such saving in heat lessening the heat required to be developed by oxidation of the more desirable hydrocarbons. The sulphur dioxide or sulphuric acid obtained by such oxidation of the sulphur and the oil may" i be employed to assist in bringing about the union of the acetaldehyde with the phenoloid bodies .or other substances required in making the resinous material of the present invention, While formaldehyde resinifles readily with for example phenol'in the presence either of an acid or an alkaline catalyst, this is not true of a number of 1 the higher aldehydes, the latter requiring in most cases an acid catalyst preferably a mineral acid to enable the reaction of resinification to take formaldehyde the principal aldehyde.

Still another possibility within the range of aldehyde production is that of treating the byproducts from cracking stills; including residual oils and still gases; hydrocarbons which have been subjected to drastic treatment under heat and pressure to yield a maximum amount of cracked gasoline. Such hydrocarbons resistant though they are to ordinary cracking processes involving merely heat and pressure may be disintegrated by the oxidizing step to yield additional motor spirit and other useful products of oxidation. I

The oxidizing agent which may be employed in the process preferably may be ordinary air, with its moisture content varying from day today. Or it may be=driedto a definite state of humidity. Onthe other hand steam may be introduced along with the air, or moisture specially introduced mother ways, or the. air may be diluted with diluent gases such as products of combustion or the nitrogen and other gases discharged from the condensing/apparatus. For treating highly resistant organic material or for securing special oxidizing effects the airmay be enriched withoxygen. In some cases still gases-from ordinary cracking stills maybe introduced inthe air. While airiat ordinary room temperature orair that has been cooled may be used, I prefer to pre- (ordinarily'l'o to 20' atmospheres above atmos- 1 aoeaess pheric pressure) the compression of the air to a' pressure, temperature and so forth. enable'the oxidation and other chemical changes to be oriented'in various directions. For example under one set of-conditions a maximum yield of, waterinsoluble products containing a large proportion of constituents useful as a motor-fuel will result,

while under a different set of conditions an increased or a predominating yield of more highly oxidized products, for example of a water-soluble type such as acids, aldehydes, solvents and the like, may be secured. It is of course an object under the preferred embodiment of the present invention to obtain a high to maximum yield of aldehydes as these constitute'the' largest item of expense in the manufacture of synthetic resins of the aldehyde-phenoloid type.

The gases leaving the condensers ordinarily contain a very high proportion of nitrogen and the latter may be purified and mixed with purifled hydrogen gas for example that obtained from the cracking of oils, natural gas, and the like, and the mixture of nitrogen and hydrogen in the proportions to form ammonia, passed under high pressure oyer an ammonia-formingcatalyst at a suitable temperature. for example 400 to 500 C. When iron is the catalyticsubstance, and some part at least of the ammonia thus obtained may From the foregoing it will appear that the Example 1. --Allow 300 parts of kerosene to drip intoa cracking furnace maintained at a temperature of 1200-1300'F. The vapors of the cracked kerosene are passedihrough an aircooled condenser where the higher boiling constituents are condensed" and collected. The lighter material is passed on to the mixing chamber consisting of a Venturi tube to be mixed with air. The mixture of air and cracked kerosene vapor is passed into a catalytic chamber containing catalyzer consisting of fragments of iron coated with 10 per cent of its weight of vanadium oxide. -The catalytic chamber is heated by means of the lead bath maintained at the desired temperature, namely 800-l000 F., by means of an; electrically-heated coil. The temperature of the exit gases varies between 455 and 750 F. The liquid products of the oxidation of the petroleum vapor are collectedby condensation and washing. React upon'the aldeu hydic constituentswith phenol as aforesaid to form resins which are readily separable from the other products.

Example 2.-Heat a body of gas oil to about 500 F. in a still adapted to withstand a pressure of well over 20 atmospheres. By means of a pressure pump force air at 15-20 atmospheres into the body of oil in the lower part so that the air passes up through a deep column of the oil in the form of small bubbles thus coming in intimate contact with the. oily material. The air is preheated to between 200 and 300 F. Allow the products from the still to pass into a condenser which should likewise be capable of l5 withstanding high pressures. The walls of the condenser may be made of copper to avoid attack by acids which would .result if steel were employed. Allow the temperature to rise spontaneously by the action of the air on the oil until it reaches say 750-800 F. Regulation may be effected by adjusting the temperature of the incoming air or the rate at which it passes through the oil. Oil may be fed continuously .into the receptacle in the upper part and the the lower part. The condensate obtained consists of two layers, an upper one containing the hydrocarbons and oxidized products insoluble in water and the lower layer containing acids, alde- 30 hydes and other substances. Wash-the hydrocarbon layer with water and add the washings to the aqueous layer. Distill the water-insoluble layer to make fractions appropriate as a motor fuel for example fractions boiling within the 35 range of ordinary gasoline or slightly higher. Make the aqueous layer slightly acid with 2 or 3 per cent of sulphuric acid and add phenol somewhat in excess of the amount required to resinify the aldehydic substances present; This 4.0 may be determined approximately by preliminary test on the small scale. Filter off the resin and any undesired excess of phenolby steam distillation. The resin may then be dissolved in a mixture of equal parts'of benzol and denatured 45 alcohol in the proportion of one,pound of resin to one or two pounds of the solvent mixture. Hexamethylenetetramine may be added and the solution employed to impregnate wood flour or other filler to make molding composition or to 50 impregnate sheets of paper which are subsequently hot pressed to obtain laminated pressboard. Or the resin may. be ground in a ball mill with asbestos, wood fiour or other filler and 5 to 10' per cent of hexamethylenetetramine. This mixture is then passed through hot milling rolls and is finally ground to yield a molding composition. The petroleum aldehydes give considerable difiiculty in most cases due to adhesion to the hot molds and such adhesion or sticking causes delay in molding besides injuring the ap-- pearance of the molded article and gradually defacing the polished surface of the mold. Ac,- cording to one phase of the present invention the adhesion may be overcome by incorporation in the molding composition -of fromabout 2 to 5 per cent of magnesium or calcium naphthenate or other fatty acid forming a water-insoluble compound with analkaline earth base, for ex-' ample, heavy oil or paraflin wax may be oxidized at about 180 C. by passing a current of air through it for a considerable period of time to obtain various fatty acids capable of forming -water-insoluble s'oaps.- Besides the naphthenates and fatty acids of petroleum origin yielding com- 7 pounds suitable for the purpose, I also-may use residues may be continuously withdrawn from 1 in whole or in part the stearates or steampalmitates, oleates and the like of various alkaline earth metals and also of other metals such as aluminum. Ordinarily at least 1 or 2 per or even more may be introduced. This may be added at any suitable stage preferably however during the mixing preliminary to treatment on the milling rolls or after the composi tion has been made up on the rolls and is being ground. While .as indicated aluminum palmitate, zinc stearate and the like may be used preferably I employ a compound the metallic portion of which does not tend to reduce the dielectric value to the same extent that the incorporation of a more metallic substance of the nature of zinc stearate would tend to bring about. Hence magnesium stearate, naphthenate and the like, or the corresponding calcium compounds or mixtures of these are preferred.

In the last described procedure, Example 2,

there is no need of a fire under the still hence the risk of overheating a still bottom is obviated. Thus it is feasible to employ pressures in excess of 30 atmospheres. Thus it becomes possible to oxidize the less heavy oils such as kerosene or easily sublimable substances such as naphthalene at pressures of 50 to 150 atmospheres. Still higher pressures for example 200 to 300 atmospheres also are contemplated. To apply such super-abnormal pressures to an ordinary direct fired still the bottom of which when coked may reach the temperature at which steel softens, would be out of question. Such super-abnormal pressures are utilizable with accompanying compactness of still and condensation apparatus and with the possibility of securing peculiar and specific oxidation effects at pressures above 35 atmospheres, such as forming specific aldehydes or obtaining a larger yield of mixed aldehydes. When treating a comparatively volatile substance at super-abnormal pressures (e. g. above 35 atmospheres) the still may be started with a heavy oil and the more volatile substance gradually fed in, the super-abnormal pressure applied being that giving the most desirable oxygen relationship (ratio of oxygen to charge in the still at any given time) for the purpose in hand. Super-abnormalpressures make possible a great variation in this oxygen relationship with consequent specific oxidizing effects- The aldehyde formation step thus embraces a process of oxidation which comprises bringing an oxygen-contain ing gas, preferably air, into intimate contact with an oxidizable organic body in a heated state at super-abnormal pressures, preferably in excess of 35 atmospheres; said organic bodybeing, for instance, a readily-volatile hydrocarbon, preferably at least in part in a liquid condition while in the oxidizing chamber.

The lower aldehydes present in the aqueous condensate from the oxidation step may be ob tained in desirable concentration by distilling the watery layer of Example 2. The first runnings contain acetaldehyde and other aldehydes; These may be separated and purified to such an extent as may be desirable. Preferably I employ the mixed aldehydes in proportions as derived but may isolate or eliminate one or more aldehydes by suitable rectification or other treatment. In some cases by such rectification 'a concentrate consisting in a large part of acetaldehyde or practically pure acetaldehyde may be obtained. Such rectification treatment however is expensive and the employment of a blend of aldehydes is more likely to yield a complex resin having desirable fluxing and flowing qualities yielding a better surface finish in the molded article, laminated pressboard or other fabricated product.

Aldehydes from the oily layer of Example 2 more often of higher molecular weight may be separated from the oil by sodium bisulphite treatment or in other ways and if desired may beincorporated with the aldehydes from the aqueous layer.

Preferably I employ an aldehydic mixture in resinification containing a major proportion of aldehyde of two or three carbon atoms and a minor proportion of aldehydes containing from for example four to ten carbon atoms. Aldehydes of low carbon atoms afford rapid curing 2Q resins, while those of a higher number of carbon atoms are less rapid but exert a co-operative effect in fiuxing or other action whic-his .not without benefit in affording improved molded surfaces and other enhanced qualities in molded therefore may be regarded as constituting a wellbalanced aldehydic blend yielding resins having qualities of commercial desirability and cheapness and differing from those of any individual resin of high purity.

As indicated however I do not limit myself to the use of the chance mixture of aldehydes constituting the direct result of petroleum oxidation but may rectify and separate to any extent desired to make resins in accordance with this invention evento the extent of using single aldehydes of substantial purity. Or I may incorporate with petroleum aldehyde various aldehydes obtained from extraneous sources such as formaldehyde, paraform, furfural, acrolein or other aldehydes or aldehydic products.

A difiiculty which I have noted, see Example 2,- is the tendency of the petroleum aldehyde resin products to stick to the molds. .This mold-adhesion may vary from time to time and differ according to the petroleum aldehyde mixture employed in making the resin, but when it exists even to a slight extent it is a highly condemnatory property. A molded article made by hot pressing is expected ,to have a uniform surface finish and scars or blotches due to. mold adhesion even though slight are objectionable. From experiments which I have caused to be conducted I find that certain metalloorganic substances, particularly basic magnesium or calcium soaps which have been made from higher organic acids and the appropriate corresponding bases by fusion and then finely pulverized overcome this mold-adhesion. 1

For example stearic acid or the commercial form which is a mixture of stearic and palmitic acid, is heated at about 150 C. with an excess vof magnesium or calcium oxideor mixtures of these. By using a slight excess of the base the reaction takes place rapidly and magnesium stearate which I preferably employ is readily obtained. Thus a proportion may be employed of one mol. (MgO) to two mols of stearic acid giving the normal stearate or preferably only one mol. of stearic acid giving the basic stearate. An excess of magnesia over that required to make the basic stearate for example 10 to per cent in excess is ordinarily not objectionable. The magnesium oxideshould be finely ground; when the fused product is obtained it is pulverized and preferably screened or air-separated in order'to employ only the finest portions. Larger particles are likely to form white spots or specks in the surface of the molded article. The finely divided basic stearate, basic naphthenate, or other basic compound of fatty acids, such for example as higher fatty acids obtained by the oxidation of petroleum or petroleum products such as parafiin wax may be incorporated in a molding powder to the extent of 1 or 2 per cent, which is usually suflicient to prevent mold adhesion. Sometimes,

however, it is necessary to employ larger quanwhich case 5 or 6 per cent or more may be added,

without greatly impairing the strength of the molded article. Less troublesome sticking may be relieved sometimes by using less than 1 per cent of the mold-adhesion relieving-agent. The latter may be added at various stages in the manufacture of the molding composition, but preferably after the resinification stage is completed and the resin is ready to be incorporated with. filler and so forth.

Mixtures of the foregoing metallo-organic compounds, including also water-insoluble resinates or basic resinates, likewise may be employed as mold-adhesion relieving-agents.

In some cases aldehydes by themselves may be resinified to make products for plastic purposes. In some cases these can be hardened. Also such aldehyde resins may be admixed with the complex resins described in the preceding text. In general however I prefer to produce the resinified aldehyde by the action of a second non-aldehydic substance of a dissimilar nature. Thus I do not preclude the use of acetone or urea as special resinifying agents for the aldehydes.

as cresylic acids and creosotes, naphthol andother hydroxylated ring compounds.

The proportion of phenoloid body preferably employed in making the resinified aldehyde is includes approximately molecule for molecule or chemical equivalents. Fusible resins are preferably obtained which may or may not besoluble in customary organic solvents. These resins may if desired be steam stilled to remove excess of reagents and to bring about some degree of hardening. Or the crude resin may be baked to harden it in case it is too soft foruse.

The resins of the present invention may be used both in hot pressing and also for cold molding operations.

vWhen employed without filler clear or slightly cloudy products may be obtained which if desired may be suitably colored. These may be machined to various shapes.

As extending bodies I may use various fillers such asthose customary in the plastic industry. These may be used in'various proportions depending on their density and physical-condition. A good proportion when using wood flour is to employ equal parts of this filler and the resin.

With asbestos the proportion of filler may be in-' various other resins such as shellac, dammar, copal, asphalt, tar pitch, gilsonite, rubber and so forth.

A special phase of 'the invention involves the process of making plastics which comprises resinifying an aldehydic fraction of petroleum oxidation products and incorporating extending bodies and a mold-adhesion relieving-agent.

Example 3.Add 3 cc. of concentrated hydrochloricacid to 300 grams of phenol. Place in a round bottom flask connected with-a reflux condenser and add gradually 150 grams of crude 'acetaldehyde of petroleum origin.

reflux for one hour and then heat in an open flask at 150 C. for 2 hours. A solid but slightly sticky resin is obtained which was found in one experiment to melt at 58 C. A soluble resin was obtained.

Some of this resin was dissolved in alcohol, 14 per cent of hexamethylenetetramine based onthe.weight of the resin added, and a quantity of wood flour equal to the weight of the resin was incorporated. The composition was dried in a vacuum dryer to a temperature flnally reaching 100 C. and thenwas ground. On hot pressing at 165 C. for 5 minutes with a' gauge pressure of 1000 pounds, the molded article stuck to the mold very badly. Made up in the same proportions'but with the addition to the composition of 2 per cent of its weight of pulverized magnesium stearate a well cured article was obtained in 5 minutes under like conditions which did not stick to the mold.

The aforesaid resin of Example 3 without other additions can be heated to 200C. for some time without becoming infusible. After heating to this temperature for 30 minutes the melting. point was raised to 71 C. (Ball and Ring method).

In case the foregoing resin is acid due to lack of complete expulsion of the sulphuric or hydrochloric acid employed, it may be neutralized with a small amount of ammonia or other alkali prior to incorporation with the mold-adhesion relieving-agent and other ingredients.

Example 4.- -Acidify 207.2 grams phenol with 2.4 cc. of strong hydrochloric acid, add gradually 36 grams of crude acetaldehyde of petroleum origin and boil under reflux for one hour. Heat in an open flask up .to 150 0., add 13.2 grams powdered" potassium carbonate and 77.4 grams furfural. Heat under reflux for 1 hour while reaction progresses as indicated by ebullition and then gradually heat in an open flask up to 150 C. keeping at this temperature for about half an crumble between the fingers.

Carrying out the foregoing a resin was obtained in one experiment which had a melting point oi 82 C. 90 grams of this resin was dissolved in an equal amount of alcohol, 12.6 grams hexamethylenetetramine added and the solution incorporated with 90gra'ms of wood flour. The composition was dried in vacuo up to 100 C., then ground in a ball mill and finally mixed with 5 per cent of basic magnesium stearate by grinding together in a pebble mill for 15 minutes. Upon hot pressing at 150-160 Q. for 5 minutes with u the gauge pressure registering 100 pounds, the molded article did not stick to the surface and was well cured; I

Molding composition, made by impregnating wood flour or analogous flller with a solution of the resin gives a somewhat voluminous product on drying and in some cases this is undesirable Boil under hour until the resin which forms will on coolin because more capacious and therefore more'expensive molds are required. The composition may be made of greater density by mixing the ingredients without solvent by passing through heated milling rolls. The sheeted composition thus obtained. 1

The following illustrates the procedure when the maximum degree of utilization of petroleum products is secured.

Example 5.React on petroleum phenoloids with admixed petroleum aldehydes using proportions which give approximately one mol. of 1 phenoloid to a mol. of aldehyde. Carry out the tion of hydrogen and nitrogen, both obtained through the instrumentality oi. the petroleum oxidation step. impregnate a filler with the foregoing solution, incorporating 2 or 3 per cent of calcium naphthenate, the naphthenic acids from which this compound is made being derived from the refining of petroleum. If electrical resistivity is not required the filler employed maybe flnely ground carbon or coke obtained from petroleum cracking operations. I

The foregoing examples of resins made in accordance with the present invention point out the particular application of such resins in the plastic industry to form the basis of molding compositions. The present application is likewise directed to the production of soluble resins from raw materials such as have been specified, these soluble resins being intended for use in the coating industry either being dissolved in volatile solvents to make coating compositions that dry simply by evaporation of the solvent, or the resins may be incorporated with drying oils such as linseed and tung oil or mixtures of these drying oils or their free fatty acids, giving an oil varnish type of resin. Likewise the resin of petroleum origin or one whose aldehydic reactivecomponent is derived from petroleum may be heated with rosinto form an oil varnish base. This method of treatment is especially desirable when a phenol aldehyde resin has. been prepared which is not of itself suillciently soluble in drying oils and in hydrocarbon solvents, especially volatile thinners from petroleum.

In Examples 3 and 4 I have referred to a resin prepared from a phenolic body;-namely phenol, and crude acetaldehyde of petroleum origin employing a small proportion of an acid as a catalyst. Resins of this type, especially those made with the aid of aldehydes of petroleum origin containing more than one carbon atom, that is, acetaldehyde and its higher homologues, may be used advantageously in the production of these phenolic resins with the object of securing increased or improved solubility of the resin in drying oils. Thus various aldehydes oi 3, 4, 5, 6 and 7 carbon atoms and upwards may be used, especially in admixture with the object of securing that increased degree of resinification which ahigher degree of complexity of resin constitution brings about. In Example5 the mixed petroleum aldehydes employed are such that the resin obtained is soluble at a, given stage in solvent material such as that which may be obtained from the aqueous distillate from Example 2. Resins of this type may be employed as such for coating purposes or they may be further reacted with rosin or tung' oil, and the like, by adequate heat treatment.

Within the field of the present invention I in clude the disclosures of my copending application Serial No. 383,167, filed August 2, 1929, and containing subject matter derived from Serial No. 22,202, and hence includes the mixed formaldehyde-acetaidehyde products particularly described in Serial No. 383,167; It likewise embraces xylenol (or the mixed xylenols) as a desirable phenolic body.

The oil-soluble resin may be made by reacting xylenol and acetaldehyde as follows:

Example 6.61 parts by weight xylenol'fraction boiling point 205-212 C., 25 parts paraldehyde, and 1 part orthophosphoric acid. The phosphoric acid was added to the xylenol and the mixture heated to about 45 C., and the paraldehyde introduced very gradually over a period of ,5 hour. The heat was cut oif almost immediately after beginning to introduce the paraldehyde and the temperature 'rose spontaneouslyto about C.

The product was washed to remove the free phosphoric acid and dried. On cooling a brownish, hard resin was obtained. 1' part oi this resin was found to dissolve readily in, for. example, 4 parts of linseed oil at a temperature or about C.

present invention the glyceride ,oils' such as the.

drying and semi-drying oils, andthe like, are intended).

Example 7.232 parts by weight acetone. 5 parts by weight concentrated hydrochloric acid. and 976 parts by weight of crude rnylenol, boiling range 205-225 C., were heated under a reflux condenser for 12 hours yielding a heavy viscous oil. The reaction was directed'to the formation of dihydroxydixylyldimethylmethane.

To v100 parts of said heavy viscous oilwithout purification 50 parts of paraldehyde were added gradually over a period of about /2 hour the temperature being carried to -100" C. The reaction product was washed and driedresulting in obtaining a sort resin which was almost completely soluble in hot linseed or tung oil or mixtures'oi these.

. In coating compositions-of the varnish type made from xylenol acetaldehyde resin, an oil of the linseed and tung oil type, a drier and a thinner,

increase in the certain I may secure a resinous component of a somewhat higher melting point by reacting on the xylenol acetaldehyde resin in solution in a drying oil by areagent such 'as formaldehyde or hexamethylenetetramine, heating the composition until the desired degree of hardness occurs without sacrifice of solubility of the product. In this way a composite resinof the acetaldehyde formaldehyde type dissolved in the linseed oil, tung oil,

and, the like, with suitable thinners, such as turpentine, is obtained which tends to give harder coatings on drying than those which have not received the formaldehyde hardening treatment. In like manner coatingcompositions may be made without the addition of hexamethylenetetramine, paraform, and. so forth, then the hardening agent added and the coating applied and baked at a reactive temperature to cause hardening to set in in the coating, to convert the resin to the desired degree.

What I claim is:

'1. The process which comprises resinifying a mixed aldehydic fraction of petroleum oxidation products containing a mixture of various aldehydes and other partial oxidation products, with a phenolic body.

2. A composite of xylenol acetaldehyde resin and drying oil, treated with ,a formaldehydeyielding component.

3. The method of producing composites which comprises treating a xylenol acetaldehyde resin in solution in a drying oil with a formaldehydeyielding agent, whereby a composite of resin and drying oil is obtained yielding hard coatings on drying from solutions containing such composites.

4. An oil-soluble resinous reaction product of xylenol with a complex mixture of water-soluble aldehydes of petroleum oxidation.

5. An oil-soluble acetone xylenol acetaldehyde condensation product exhibiting marked solubility in drying oils. I

6. A fusible condensation product from the complex mixed aldehydes of petroleum oxidation and a xylenoi distillate having an initial boiling point of between 200 and 205 C., about 50% of which distillate distills over at a temperature up to 212 C.

'7. A base-catalyzed resinous condensation product of complex mixed aldehydes of petroleum oxidation and crude coal tar.acids, including a substantial amount of xylenol.

8. A resinous condensation product containing a hard, substantially infusible condensation product of complex mixed aldehydes of petroleum oxidation, and coal tar acids including a substantial amount of xylenol, and a fibrous filler. 1

9.A resinous condensation product from a mixed aldehydic fraction of petroleum oxidation products containing a mixture of various aldehydes and other partial oxidation products, with a phenolic body.

10. The method of producing a iusible condensation product which comprises resinifying the complex mixed aldehydes of petroleum oxidation, and a xylenol distillate havinganinitial boiling point of between 200 and 205 C., about 50% of which distillate distills over at a temperature up to 212 C. CARLE'I'ON ELLIS. 

